Certain phenyl sulfonamide polymers have been known at least since the late 1960""s. R. W. Angelo et al., in IBM Technical Disclosure Bulletin, vol. 11, No. 7 (December 1968), disclosed condensing m-benzene disulfonyl chloride with hexamethylene diamine to form a phenyl sulfonamide polymer. Said publication further disclosed crosslinking polystyrene with then sulfonamide linkages which in turn can be treated to form the corresponding sulfonic acid or acid chloride which, when treated with a diamine such as hexamethylene diamine, forms a polystyrene sulfonamide.
European Patent Application published on Sep. 11, 1996, EP 0 731 388 A2, discloses styryl and methacryl-based sulfornamide-containing polymers. T. X. Neenan et al., Microelectronics Technology, ACS Symposium Series 614, (April 2-6, 1995), pp. 194-206, also discuss styrylmethylsulfonamides. These specific polymers are said to be useful as photoresists, but they are deficient because they are not easily soluble in photoresist compatible solvents, such as propyleneglycol methyl ether acetate. PCT Patent Application published Sep. 12, 1997, WO 97/33198, discloses addition-type polymers of norbornene-type monomers, some containing functional groups such as carboxyl groups or esters, that may be obtained by polymerizing such monomers in the presence of Group VIII metal catalysts. European Patent Application published Aug. 13, 1997, EP 0 789 278 A2, discloses ROMP polymers obtained by polymerizing norbornene-type monomers that may contain functional substituents other than sulfonamides, by using well known metathesis catalysts. European Patent Application published Sep. 10, 1997, EP 0 794 458 A2, discloses the preparation of cyclic olefin copolymers, such as a norbornene/maleic anhydride and norbornene/maleic anhydride/acrylate, using free radical polymerization. None of the above mentioned publications disclose NB sulfonamides.
The preparation of fluorine-containing sulfonamide norbornenes is described by A. O. Kas""yan et al., Ukr. Gos. Khim-Tekhnol. Univ., Dnepropetrovsk, Ukraine, Zh. Org. Khim. (1995), 357-64. CODEN:ZORKAE; ISS 0514-7492. CAN 124:145481.
It is a general object of the invention to provide novel sulfonamide norbornene (NB) polymer compositions. Such polymers may be NB sulfonamide homopolymers or copolymers of at least one NB sulfonamide with at least one other comonomer such as NB, ethylene, an acrylate, maleic anhydride, CO, SO2, and the like.
It is another object of the invention to provide certain novel NB sulfonamide monomers.
The addition homopolymers and copolymers of this invention may be prepared employing a single or multicomponent catalyst system, each containing a Group VIII metal ion source. Copolymers of an NB sulfonamide and maleic anhydride or SO2 or maleic anhydride and an acrylate may be prepared employing a standard free radical catalyst. NB sulfonamide ROMP polymers may be prepared employing known ROMP catalysts and thereafter preferably hydrogenating the resulting polymer.
The polycyclic copolymers of the present invention comprise repeating units copolymerized from at least one polycycloolefin monomer wherein at least a portion of which contain a pendant sulfonamide group. As stated herein the terms xe2x80x9cpolycycloolefin,xe2x80x9d xe2x80x9cpolycyclic,xe2x80x9d and xe2x80x9cnorbornene-typexe2x80x9d monomer are used interchangeably and mean that the monomer contains at least one norbornene-type moiety as shown below: 
In the formula above, x represents oxygen, nitrogen with a substituent being hydrogen or C1-10 alkyl, linear or branched, sulfur or a methylene group of the formula xe2x80x94(CH2)nxe2x80x2xe2x80x94 wherein nxe2x80x2 is an integer of 1 to 5.
The simplest polycyclic monomer of the invention is the bicyclic monomer, bicyclo[2.2.1]hept-2-ene, commonly referred to as norbornene. The term norbornene-type monomer is meant to include substituted and unsubstituted norbornene-type monomers, and any substituted and unsubstituted higher cyclic derivatives thereof so long as the monomer contains at least one norbornene-type or substituted norbornene-type moiety. The substituted norbornene-type monomers and higher cyclic derivatives thereof contain a pendant hydrocarbyl substituent(s) or a pendant functional substituent(s) containing a heteroatom such as oxygen or nitrogen.
The sulfonamide functional norbornene-type monomers are represented by the structure below: 
wherein x represents oxygen, nitrogen with hydrogen or C1-10 alkyl substituent, sulfur or a methylene group of the formula xe2x80x94(CH2)nxe2x80x2xe2x80x94; n is an integer of 0, 1 or more, preferably 0 to 5, and more preferably 0, 1, or 2; and R1 and R4 independently represent hydrogen, linear or branched linear and branched C1-C20 alkyl (preferably C1-10); R2 and R3 independently represent hydrogen, linear and branched C1-C20 alkyl or a sulfonamide group, with the proviso that at least one of R2 and R3 is a pendant sulfonamide group of the formulae:
xe2x80x83xe2x80x94Axe2x80x94NRxe2x80x2SO2Rxe2x80x3 and xe2x80x94Axe2x80x94SO2NRxe2x80x2Rxe2x80x2xe2x80x3
or a cyclic sulfonamide group formed by combining R2 and R3 together with the two ring carbon atoms to which they are attached to form a heterocyclic ring of the formula: 
wherein in the above structures m is an integer from 1 to 3;
Rxe2x80x2 represents hydrogen, linear and branched tri(C1-C10) alkylsilyl, xe2x80x94C(O)CF3, xe2x80x94C(O)OR, and xe2x80x94OC(O)OR, wherein R is lnear and branched C1-C10 alkyl, preferably t-butyl, linear and branched C1-C10 haloalkyl, substituted and unsubstituted C6-C14 aryl, and substituted and unsubstituted C7-C20 aralkyl. As used here and throughout the specification the term substituted cycloalkyl, aryl (e.g., phenyl), and aralkyl means that the respective rings can contain monosubstitution or multisubstitution and the substituents are independently selected from linear and branched C1-C5 alkyl, linear and branched C1-C5 haloalkyl, substituted and unsubstituted phenyl, and halogen, preferably, chlorine and fluorine;
Rxe2x80x3 represents linear and branched C1-C10 alkyl, linear and branched C1-C10 haloalkyl, xe2x80x94(CHRxe2x80x2)nxe2x80x3xe2x80x94COOR, xe2x80x94(CHR1xe2x80x2)nxe2x80x3xe2x80x94OR, xe2x80x94(CHR1xe2x80x2)nxe2x80x3xe2x80x94C(O)R, substituted and unsubstituted C3 to C8 cycloalkyl(as defined above), xe2x80x94(CHRxe2x80x2)nxe2x80x3 cyclic esters (lactones) containing 2 to 8 carbon atoms (not counting the carbonyl carbon), xe2x80x94(CHRxe2x80x2)nxe2x80x3 cyclic ketones containing 4 to 8 carbon atoms (not counting the carbonyl carbon), cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein R, R1xe2x80x2, and nxe2x80x3 are as defined above;
Rxe2x80x2xe2x80x3 represents hydrogen, linear and branched C1-C10 alkyl, linear and branched C1-C10 haloalkyl, xe2x80x94C(O)OR, xe2x80x94(CHR1xe2x80x2)nxe2x80x3xe2x80x94OR, xe2x80x94(CHR1xe2x80x2)nxe2x80x3xe2x80x94C(O)R, substituted and unsubstituted C3 to C8 cycloalkyl(as defined above), xe2x80x94(CHRxe2x80x2)nxe2x80x3 cyclic esters (lactones) containing 2 to 8 carbon atoms (not counting the carbonyl carbon), xe2x80x94(CHRxe2x80x2)nxe2x80x3 cyclic ketones containing 4 to 8 carbon atoms (not counting the carbonyl carbon), cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein R, R1xe2x80x2, and nxe2x80x3 are as defined above
Monomers containing the foregoing group can be represented by Formula I(a) below: 
In Formula I(a) x, R1, R4, n and m are as defined previously above. In Formula Ia R1 and, R4 are preferably hydrogen.
In the formulae above xe2x80x94Axe2x80x94 is a divalent radical selected from xe2x80x94(CR1xe2x80x2R2xe2x80x2)nxe2x80x3xe2x80x94; xe2x80x94(CHR1xe2x80x2)nxe2x80x3O(CHR1xe2x80x2)nxe2x80x3xe2x80x94; xe2x80x94(CHR1xe2x80x2)nxe2x80x3C(O)O(CHR1xe2x80x2)nxe2x80x3xe2x80x94; xe2x80x94(CHR1xe2x80x2)nxe2x80x3C(O)(CHR1xe2x80x2)nxe2x80x3xe2x80x94; C3-C8 cycloalkyl; C6-C14 aryl; cyclic ethers and cyclic diethers containing 4 to 8 carbon atoms, wherein nxe2x80x3 represents an integer from 1 to 10, and R1xe2x80x2 and R2xe2x80x2 independently represent hydrogen, linear and branched C1-C10 alkyl and halogen, preferably chlorine and fluorine. Divalent radical xe2x80x94Axe2x80x94 represents the group xe2x80x94(CHR1xe2x80x2)nxe2x80x3OC(O)xe2x80x94 only when the sulfonamide group is xe2x80x94NRxe2x80x2SO2Rxe2x80x3.
The divalent cycloalkyl radicals include substituted and unsubstituted C3 to C8 cycloalkyl moieties represented by the formula: 
wherein xe2x80x9caxe2x80x9d is an integer from 2 to 7 and optionally Rq which, when present, represents linear and branched C1-C10, alkyl groups, linear and branched C1-C10 haloalkyl, and halogen, preferably chlorine and fluorine. As used here and throughout the specification the term haloalkyl means that at least one hydrogen atom on the alkyl radical is replaced by a halogen. The degree of halogenation can range from at least one hydrogen atom being replaced by a halogen atom (e.g., a monofluoromethyl group) to full halogenation (perhalogenation) wherein all hydrogen atoms on the alkyl group have been replaced by a halogen atom (e.g., trifluoromethyl (perfluoromethyl)). Preferred divalent cycloalkylene radicals include cyclopentylene and cyclohexylene moieties represented by the following structures: 
wherein Rq is defined above. As illustrated here and throughout this specification, it is to be xe2x80x94(CHRxe2x80x2)nxe2x80x3 understood that the bond lines projecting from the cyclic structures and/or formulae represent the divalent nature of the moiety and indicate the points at which the carbocyclic atoms are bonded to the adjacent molecular moieties defined in the respective formulae. As is conventional in the art, the diagonal bond line projecting from the center of the cyclic structure indicates that the bond is optionally connected to any one of the carbocyclic atoms in the ring. It is also to be understood that the carbocyclic atom to which the bond line is connected will accommodate one less hydrogen atom to satisfy the valence requirement of carbon.
The divalent aryl radicals include substituted and unsubstituted aryl moieties. A representative divalent aryl moiety is shown below. 
wherein Rq is as defined above. In the above formulae R1xe2x80x2 and R2xe2x80x2 independently represent linear and branched C1-C10 alkyl, linear and branched C1-C10 haloalkyl, and halogen selected from chlorine, bromine, fluorine, and iodine, preferably fluorine.
The divalent cyclic ethers and diethers can be represented by the formulae: 
The norbornene-type monomers of Formula I can be copolymerized with hydrocarbyl and/or functionally substituted norbornene-type monomer(s) represented by Formula II below: 
wherein R5 to R8 independently represents a hydrocarbyl or functional substituent and n is an integer of 0, 1 or more, preferably 0 to 5.
When the substituent is a hydrocarbyl group R5 to R8 independently represent hydrogen, linear and branched C1-C10 alkyl, linear and branched C1-C10 haloalkyl, linear and branched, C2-C10 alkenyl, linear and branched C2-C10 alkynyl, C5-C12 cycloalkyl, C6-C12 aryl, and C7-C24 aralkyl; R6 and R8 together with the two ring carbon atoms to which they are attached can represent a cycloaliphatic group containing 4 to 12 carbon atoms or an aryl group containing 6 to 14 carbon atoms. The cycloalkyl, cycloaliphatic, aryl, and aryl groups set forth above can optionally be substituted with linear and branched C1-C5 alkyl, linear and branched C1-C5 haloalkyl, C5-C12 cycloalkyl, C6-C12 aryl, and halogen, preferably chlorine and fluorine.
When the pendant group(s) is a functional substituent, R5 to R8 independently represent a radical selected from xe2x80x94(CH2)nC(O)OR9, xe2x80x94(CH2)nxe2x80x2xe2x80x3C(O)OR9, xe2x80x94(CH2)nxe2x80x2xe2x80x3OR9, xe2x80x94(CH2)nxe2x80x2xe2x80x3OC(O)R9, xe2x80x94(CH2)nxe2x80x2xe2x80x3C(O)R9, xe2x80x94(CH2)nxe2x80x2xe2x80x3OC(O)OR9, and xe2x80x94(CH2)nxe2x80x2xe2x80x3C(O)OR10, wherein nxe2x80x2xe2x80x3 independently represents an integer from 0 to 10; R9 independently represents hydrogen, linear and branched C1-C10 alkyl, linear and branched C1-C10 haloalkyl, linear and branched C2-C10 alkenyl, linear and branched C2-C10 alkynyl, substituted and unsubstituted C5-C12 cycloalkyl, substituted and unsubstituted C6-C14 aryl, and substituted and unsubstituted C7-C24 aralkyl; R10 represents a moiety selected from xe2x80x94C(CH3)3,xe2x80x94Si(CH3)3, xe2x80x94CH(R11)OCH2CH3, xe2x80x94CH(R11)OC(CH3)3 or the following alicyclic and hetero cyclic groups: 
wherein R11 represents hydrogen or a linear and branched C1-C5 alkyl group. The alkyl groups include methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, t-pentyl and neopentyl. In the above structures, the single bond line projecting from the cyclic groups indicates the position where the cyclic protecting group is bonded to the acid substituent. Examples of R10 radicals include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoyl, 3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, and 1-t-butoxyethyl. It is preferable that only two above defined functional substituents be present and most preferably only one.
The R10 radical can also represent dicyclopropylmethyl (Dcpm), and dimethylcyclopropylmethyl (Dmcp) groups which are represented by the following structures: 
Other monomers that can be copolymerized with the norbornene-type monomers of Formula I are maleic anhydride, SO2, CO, acrylate and methacrylate monomers represented by the formulae CH2xe2x95x90CHR12C(O)OR10 and CH2xe2x95x90CHR12C(O)OR13, wherein R12 is hydrogen or methyl, R13 is a sulfonamide group represented by
xe2x80x83xe2x80x94Axe2x80x94NRxe2x80x2SO2Rxe2x80x3 and xe2x80x94Axe2x80x94SO2NRxe2x80x2Rxe2x80x2xe2x80x3
wherein xe2x80x94Axe2x80x94, Rxe2x80x2, Rxe2x80x3, and Rxe2x80x2xe2x80x3 are as previously defined above, and R10 is as defined above, and maleimides of the formula: 
wherein R14 represents hydrogen, linear and branched C1-C10 alkyl, substituted and unsubstituted cycloalkyl, and substituted and unsubstituted C6-C14 aryl.
The polymers of the invention comprise repeating units polymerized from at least one monomer(s) of Formula I in optional combination with a monomer(s) selected from Formula II, maleic anhydride, sulfur dioxide (SO2), carbon monoxide (CO), an acrylate monomer(s) defined above and combinations thereof.
The acrylate and methacrylate comonomers of this invention are represented by the formula CH2xe2x95x90CHR8C(O)OR9, wherein R8 is hydrogen or methyl and R9 is selected from hydrogen, linear and branched (C1-C10) alkyl, linear and branched, (C2-C10) alkenyl, linear and branched (C2-C10) alkynyl, (C5-C12) cycloalkyl, (C6-C14) aryl, and (C7-C24) aralkyl. Representative alkyl groups include but are not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Representative alkenyl groups include but are not limited to vinyl, and allyl. Representative alkynyl groups include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representative cycloalkyl groups include but are not limited to cyclopentyl, cyclohexyl, and cyclooctyl substituents. Representative aryl groups include but are not limited to phenyl, naphthyl and anthracenyl. Representative aralkyl groups include but are not limited to benzyl, and phenethyl. As discussed above, the hydrocarbyl groups include halogenated and perhalogenated hydrocarbyl substituents. The preferred perhalohydrocarbyl groups include perhalogenated phenyl and alkyl groups. The alkyl groups are linear or branched and have the formula Czxe2x80x94X2Z+1 wherein X is a halogen and z is selected from an integer from 1 to 10. Preferably X is fluorine. Preferred perfluorinated substituents include perfluorophenyl, perfluoromethyl, perfluoroethyl, perfluoropropyl, and perfluobutyl. In addition to the halogen substituents, the cycloalkyl and aryl groups of the invention can be further substitued with linear and branched (C1-C5) alkyl and haloalkyl groups, aryl groups and cycloalkyl groups.
In the acrylate and methacrylate formulae above, R9 also represents an acid labile moiety selected from xe2x80x94C(CH3)3, xe2x80x94Si(CH3)3, xe2x80x94CH(R7)OCH2CH3, xe2x80x94CH(R7)OC(CH3)3 or the following cyclic groups: 
wherein R7 is the same as defined above. Representative groups defined under R9 include 1-methyl-1-cyclohexyl, isobornyl, 2-methyl-2-isobornyl, 2-methyl-2-adamantyl, tetrahydrofuranyl, tetrahydropyranoly, 3-oxocyclohexanonyl, mevalonic lactonyl, 1-ethoxyethyl, and 1-t-butoxy ethyl groups. R9 can also represent the Dcpm and Dmcp groups defined above.
There are several routes to polymerize the NB sulfonamide monomers. These include: (1) ring-opening metathesis polymerization (ROMP); (2) ROMP followed by hydrogenation; and (3) addition polymerization. Each of the foregoing routes produces polymers with specific structures as shown in the diagram 1 below. The sulfonamide groups are present but are not indicated in the structures shown below. 
A ROMP polymer has a different structure than that of an addition polymer. A ROMP polymer contains a repeat unit with one less cyclic unit than did the starting monomer. The repeat units are linked together in an unsaturated backbone as shown above. Because of this unsaturation the polymer preferably should subsequently be hydrogenated to confer oxidative stability to the backbone. Addition polymers on the other hand have no Cxe2x95x90C unsaturation in the polymer backbone despite being formed from the same monomer.
The ROMP polymers of the present invention are polymerized in the presence of a metathesis ring-opening polymerization catalyst in an appropriate solvent. Methods of polymerizing via ROMP and the subsequent hydrogenation of the ring-opened polymers so obtained are disclosed in the U.S. Pat. Nos. 5,053,471 and 5,202,388 which are incorporated herein by reference. In these patents the monomers that are polymerized and the resulting polymers do not contain sulfonamide groups, but the methods disclosed there can be used to polymerize the NB sulfonamides.
In one ROMP embodiment the polycyclic monomers of the invention can be polymerized in the presence of a single component ruthenium or osmium metal carbene complex catalyst such as those disclosed in WO 95-US9655. The monomer to catalyst ratio employed should range from about 100:1 to about 2,000:1, with a preferred ratio of about 500:1. The reaction can be conducted in halohydrocarbon solvent such as dichlorethane, dichloromethane, chlorobenzene and the like or in a hydrocarbon solvent such as toluene. The amount of solvent employed in the reaction medium should be sufficient to achieve a solids content of about 5 to about 40 weight percent, with 6 to 25 weight percent solids to solvent being preferred. The reaction can be conducted at a temperature ranging from about 0xc2x0 C. to about 60xc2x0 C., with about 20xc2x0 C. to 50xc2x0 C. being preferred.
A preferred metal carbene catalyst is bis(tricyclohexylphosphine)benzylidene ruthenium. Surprisingly and advantageously, it has been found that this catalyst can be utilized as the initial ROMP reaction catalyst and as an efficient hydrogenation catalyst to afford an essentially saturated ROMP polymer. No additional hydrogenation catalyst need be employed. Following the initial ROMP reaction, all that is needed to effect the hydrogenation of the polymer backbone is to maintain hydrogen pressure over the reaction medium at a temperature above about 100xc2x0 C. but lower than about 220xc2x0 C., preferably between about 150 to about 200xc2x0 C.
The NB sulfonamide monomers can also be homopolymerized or copolymerized with maleic anhydride or with sulfur dioxide (SO2) or with maleic amhydride and an acrylate using a standard free radical initiator. Typical free radical initiators are peroxygen compounds and persulfates, particularly benzoyl peroxide, t-butyl diperphthalate, perargouyl peroxide, 1-hydroxycyclohexyl hydroperoxide and other hydroperoxides, dialkylperoxides and diacylperoxides; azo compounds such as azodiisobutyronitrile and dimenthylazodi-isobutyromitrile and other free radical initiators known in the art. Free radical polymerization techniques are set forth in the Encyclopedia of Polymer Science, John Wiley and Sons, 13, 708 (1988).
Useful solvents include, for example, alkanes such a n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; halogenated hydrocarbons such as chlorobutane, bromohexane, dichloroethane, hexamethylene dibromide and chlorobenzene; and saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, I-butyl acetate, and methyl propionate, and tetrahydrofuran.
The norbornene monomers that are copolymerized with NB sulfonamides may contain acid-cleavable estere groups. Examples of such groups are a linear acetal group such as methoxymethyloxy, ethoxymethyloxy, n-propoxymethyloxy, isopropoxymethyloxy, n-butoxymethyloxy, t-butoxymethyloxy, phenaxymethloxy and trichloroethoxymethyloxy groups; a cyclic acetal group such as tetrahydrofuranyloxy and tetrahydropyranyloxy; a carbonate group such as isopropoxycarbonyloxy, 2-butenyloxycarbonyloxy, t-butoxycarbonyloxy, 1-methyl-2-propenyloxycarbonyloxy, cyclohexyloxycarbonloxy and 2-cyclohexenyloxycarbonyloxy groups; an orthocarbonate group such as trimethoxymethyloxy, triethaxymethyloxy, tri-n-propoxymethyloxy and methoxydiethoxymethyloxy; a (cyclo)alkyl ether such as methyl ether, ethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, 2-methylpropyl ether, 1-methylrpopyl ether, t-butyl ether, cyclohexyl ether and t-butylcyclohexyl ether groups; an alkenyl ether such as allyl ether, 2-butenyl ether, 2-cyclohexenyl ether and 1-methyl-2-propenyl ether groups; an aralkyl ether such as benzyl ether and t-butyl benzyl ether groups; and an enol ether such as vinyl ether, 1-propenyl ether, 1-butenyl ether, 1,3-butadienyl ether and phenylvinyl ether. The ester groups may also be converted into a carboxyl group or a hydroxyl group.
Alternatively, and preferably, the monomers of this invention are polymerized in the presence of a single or multicomponent catalyst system comprising a Group VIII metal ion source. The above described NB sulfonamide monomers may be addition homopolymerized or addition copolymerized with one or more other NB sulfonamide monomers or with one or more other above described monomers, such as non-sulfonamide containing norbornenes, acrylates or methacrylates, CO, or ethylene. Such addition polymerizations may be carried out in the presence of a single or multicomponent catalyst system comprising a group VIII metal ion source (preferably palladium or nickel). Surprisingly, it has been found that the addition polymers so produced possess excellent transparency to deep UV light (193 nm) and exhibit excellent resistance to reactive ion etching.
In one embodiment, the single component catalyst system of this invention comprises a Group VIII metal cation complex and a weakly coordinating counteranion as represented by the following formula: 
wherein L represents a ligand containing 1, 2, or 3 xcfx80-bonds; M represents a Group VIII transition metal; X represents a ligand containing 1 "sgr"-bond and between 0 to 3 xcfx80-bonds; y is 0, 1, or 2 and z is 0 or 1 and wherein y and z cannot both be 0 at the same time, and when y is 0, a is 2 and when y is 1, a is 1; and CA is a weakly coordinating counteranion.
The phrase xe2x80x9cweakly coordinating counteranionxe2x80x9d refers to an anion which is only weakly coordinated to the cation, thereby remaining sufficiently labile to be displaced by a neutral Lewis base. More specifically the phrase refers to an anion which when functioning as a stabilizing anion in the catalyst system of this invention does not transfer an anionic substituent or fragment thereof to the cation, thereby forming a neutral product. The counteranion is non-oxidative, non-reducing, non-nucleophilic, and relatively inert.
L is a neutral ligand that is weakly coordinated to the Group VIII metal cation complex. In other words, the ligand is relatively inert and is readily displaced from the metal cation complex by the inserting monomer in the growing polymer chain. Suitable xcfx80-bond containing ligands include (C2 to C12) monoolefinic (e.g., 2,3-dimethyl-2-butene), dioolefinic (C4 to C12) (e.g., norbornadiene) and (C6 to C20) aromatic moieties. Preferably ligand L is a chelating bidentate cyclo(C6 to C12) diolefin, for example cyclooctadiene (COD) or dibenzo COD, or an aromatic compound such as benzene, toluene, or mesitylene.
Group VIII metal M is selected from Group VIII metals of the Periodic Table of the Elements. Preferably M is selected from the group consisting of nickel, palladium, cobalt, platinum, iron, and ruthenium. The most preferred metals are nickel and palladium.
Ligand X is selected from (i) a moiety that provides a single metal-carbon "sgr"-bond (no xcfx80-bonds) to the metal in the cation complex or (ii) a moiety that provides a single metal carbon "sgr"-bond and 1 to 3 xcfx80-bonds to the metal in the cation complex. Under embodiment (i) the moiety is bound to the Group VIII metal by a single metal-carbon "sgr"-bond and no xcfx80-bonds. Representative ligands defined under this embodiment include (C1 to C10) alkyl moieties selected from methyl, ethyl, linear and branched moieties such as propyl, butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl and (C7 to C15) aralkyl such as benzyl. Under embodiment (ii) generally defined above, the cation has a hydrocarbyl group directly bound to the metal by a single metal-carbon "sgr"-bond, and also by at least one, but no more than three xcfx80-bonds. By hydrocarbyl is meant a group that is capable of stabilizing the Group VIII metal cation complex by providing a carbon-metal "sgr"-bond and one to three olefinic xcfx80-bonds that may be conjugated or non-conjugated. Representative hydrocarbyl groups are (C3 to C20) alkenyl which may be non-cyclic, monocyclic, or polycyclic and can be substituted with linear and branched (C1 to C20) alkoxy, (C6 to C15) aryloxy or halo groups (e.g., Cl and F).
Preferably X is a single allyl ligand, or, a canonical form thereof, which provides a "sgr"-bond and a xcfx80-bond; or a compound providing at least one olefinic xcfx80-bond to the metal, and a "sgr"-bond to the metal from a distal carbon atom, spaced apart from either olefinic carbon atom by at least two carbon-carbon single bonds (embodiment iii).
It should be readily apparent to those skilled in the art that when ligand L or X is absent (i.e., y or z is zero), the metal cation complex will be weakly ligated by the solvent in which the reaction was carried out. Representative solvents include, but are not limited to, halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane and aromatic solvents such as benzene, toluene, mesitylene, chlorobenzene, and nitrobenzene, and the like. A more detailed discussion on appropriate solvents will follow.
Selected embodiments of the Group VIII metal cation complexes of the single component catalyst systems of this invention are shown below.
Structure VII illustrates embodiment (i) wherein ligand X is a methyl group that is bound to the metal via a single metal-carbon "sgr"-bond, and ligand L is COD that is weakly coordinated to the palladium metal via two olefinic xcfx80-bonds. In the structure below M preferably represents palladium or nickel. 
Structures VIII, IX, and X illustrate various examples of embodiment (ii) wherein X is an allyl group that is bound to the metal (palladium is shown for illustrative purposes only) via a single metal-carbon xcfx80-bond and at least one but no more than three xcfx80-bonds.
In Structure VIII, L is not present but an aromatic group providing three xcfx80-bonds is weakly coordinated to the palladium metal; X is an allyl group providing a single metal-carbon xcfx80-bond and an olefinic xcfx80-bond to the palladium.
In Structure IX, L is COD and X is an allyl group providing a metal-carbon "sgr"-bond and an olefinic xcfx80-bond to the palladium.
Structure X illustrates an embodiment wherein ligand X is an unsaturated hydrocarbon group that provides a metal-carbon "sgr"-bond, a conjugated xcfx80-bond and two additional xcfx80-bonds to the palladium; L is absent. 
Substituents R20, R21, R22 will be described in detail below.
Structures XI and XII illustrate examples of embodiment (iii) wherein L is COD and X is a ligand that provides at least one olefinic xcfx80-bond to the Group VIII metal and a "sgr"-bond to the metal from a distal carbon atom, spaced apart from either olefinic carbon atom by at least two carbon-carbon single bonds. 
The above-described Group VIII cation complexes are associated with a weakly coordinating or non-coordinating counteranion, CAxe2x88x92, which is relatively inert, a poor nucleophile and provides the cation complex with essential solubility in the reaction solvent. The key to proper anion design requires that it be labile, and stable and inert toward reactions with the cationic Group VIII metal complex in the final catalyst species and that it renders the single component catalyst soluble in the solvents of this invention. The anions which are stable toward reactions with water or Brxc3x8nsted acids, and which do not have acidic protons located on the exterior of the anion (i.e., anionic complexes which do not react with strong acids or bases) possess the stability necessary to qualify as a stable anion for the catalyst system. The properties of the anion which are important for maximum lability include overall size, and shape (i.e., large radius of curvature), and nucleophilicity.
In general, a suitable anion may be any stable anion which allows the catalyst to be dissolved in a solvent of choice, and has the following attributes: (1) the anion should form stable salts with the aforementioned Lewis acid, Brxc3x8nsted acids, reducible Lewis Acids, protonated Lewis bases, thallium and silver cations; (2) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; (3) the anion should be a relatively poor nucleophile; and (4) the anion should not be a powerful reducing or oxidizing agent.
Anions that meet the foregoing criteria can be selected from the group consisting of a tetrafluoride of Ga, Al, or B; a hexafluoride of P, Sb, or As; perfluoro-acetates, propionates and butyrates, hydrated perchlorate; toluene sulfonates, and trifluoromethyl sulfonate; and substituted tetraphenyl borate wherein the phenyl ring is substituted with fluorine or trifluoromethyl moieties. Selected examples of counteranions include BF4xe2x88x92, PF6xe2x88x92, AlF3O3SCF3xe2x88x92, SbF6xe2x88x92, SbF5SO3Fxe2x88x92, AsF6xe2x88x92, trifluoroacetate (CF3CO2xe2x88x92), pentafluoropropionate (C2F5CO2xe2x88x92), heptafluorobutyrate (CF3CF2CF2CO2xe2x88x92), perchlorate (ClO4xe2x88x92.H2O), p-toluene-sulfonate (p-CH3C6H4SO3xe2x88x92) and tetraphenyl borates represented by the formula: 
wherein RIV independently represents hydrogen, fluorine and trifluoromethyl and w is 1 to 5.
A preferred single component catalyst of the foregoing embodiment are represented by the formula: 
The catalyst comprises a -allyl Group VIII metal complex with a weakly coordinating counteranion. The allyl group of the metal cation complex is provided by a compound containing allylic functionality which functionality is bound to the M by a single carbon-metal -bond and an olefinic -bond. The Group VIII metal M is preferably selected from nickel and palladium with palladium being the most preferred metal. Surprisingly, it has been found that these single component catalysts wherein M is palladium and the cation complex is devoid of ligands other than the allyl functionality (i.e., Ly=0), exhibit excellent activity for the polymerization of functional polycyclic monomers such as the silyl containing monomers of this invention. As discussed above, it will be understood that the catalysts are solvated by the reaction diluent which diluent can be considered very weak ligands to the Group VIII metal in the cation complex.
Substituents R20, R21, and R22 on the allyl group set forth above in Structures VIII, IX and XIII are each independently hydrogen, branched or unbranched (C1 to C5) alkyl such as methyl, ethyl, n-propyl, isopropyl, and t-butyl, (C6 to C14) aryl, such as phenyl and naphthyl, (C7 to C10) aralkyl such as benzyl, xe2x80x94COORxe2x80x216, xe2x80x94(CH2)nOR16, Cl and (C5 to C6) cycloaliphatic, wherein R16 is (C1 to C5) alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl and i-butyl, and w is 1 to 5.
Optionally, any two of R20, R21, and R22 may be linked together to form a cyclic- or multi-cyclic ring structure. The cyclic ring structure can be carbocyclic or heterocyclic. Preferably any two of R20, R21, and R22 taken together with the carbon atoms to which they are attached form rings of 5 to 20 atoms. Representative heteroatoms include nitrogen, sulfur and carbonyl. Illustrative of the cyclic groups with allylic functionality are the following structures: 
wherein R23 is hydrogen, linear or branched (C1 to C5) alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and pentyl, R24 is methylcarbonyl, and R25 is linear or branched (C1 to C20) alkyl. Counteranion CAxe2x88x92 is defined as above.
Additional examples of -allyl metal complexes are found in R. G. Guy and B. L. Shaw, Advances in Inorganic Chemistry and Radiochemistry, Vol. 4, Academic Press Inc., New York, 1962; J. Birmingham, E. de Boer, M. L. H. Green, R. B. King, R. Kxc3x6ster, P. L. I. Nagy, G. N. Schrauzer, Advances in Organometallic Chemistry, Vol. 2, Academic Press Inc., New York, 1964; W. T. Dent, R. Long and A. J. Wilkinson, J. Chem. Soc., (1964) 1585; and H. C. Volger, Rec. Trav. Chim. Pay Bas, 88 (1969) 225; which are all hereby incorporated by reference.
The single component catalyst of the foregoing embodiment can be prepared by combining a ligated Group VIII metal halide component with a salt that provides the counteranion for the subsequently formed metal cation complex. The ligated Group VIII metal halide component, counteranion providing salt, and optional -bond containing component, e.g., COD, are combined in a solvent capable of solvating the formed single component catalyst. The solvent utilized is preferably the same solvent chosen for the reaction medium. The catalyst can be preformed in solvent or can be formed in situ in the reaction medium.
Suitable counteranion providing salts are any salts capable of providing the counteranions discussed above. For example, salts of sodium, lithium, potassium, silver, thallium, and ammonia, wherein the anion is selected from the counteranions (CAxe2x88x92) defined previously. Illustrative counteranion providing salts include TIPF6, AgPF6, AgSbF6, LiBF4, NH4PF6, KAsF6, AgC2F5CO2, AgBF4AgCF3CO2, AgClO4H2O, AgAsF6, AgCF3CF2CF2CO2, AgC2F5CO2, (C4H9)4NB(C6F5)4, and 
The specific catalyst: [allyl-Pd-COD]+ PF6xe2x88x92 is preformed by forming a ligated palladium halide component, i.e., bis(allyl Pd bromide), which is then subjected to scission with a halide abstracting agent in the form of a counteranion providing salt, i.e., TIPF6 in the presence of COD. The reaction sequence is written as follows: 
When partitioned, only one COD ligand remains, which is bonded by two -bonds to the palladium. The allyl functionality is bonded by one metal-carbon -bond and one -bond to the palladium.
For the preparation of the preferred -allyl Group VIII metal/counteranion single component catalysts represented in Structure XIII above, i.e., when M is palladium, allylpalladium chloride is combined with the desired counteranion providing salt, preferably silver salts of the counteranion, in an appropriate solvent. The chloride ligand comes off the allyl palladium complex as a precipitate of silver chloride (AgCl) which can be filtered out of the solution. The allylpalladium cation complex/counteranion single component catalyst remains in solution. The palladium metal is devoid of any ligands apart from the allylic functionality.
An alternative single component catalyst that is useful in the present invention is represented by the formula below:
Pd[R27CN]4[CA xe2x88x92]2
wherein R27 independently represents linear and branched (C1 to C10) alkyl and CAxe2x88x92 is a counteranion defined as above.
Another single component catalyst system useful in making polymers utilized in this invention is represented by the formula:
EnNi(C6F5)2
wherein n is 1 or 2 and E represents a neutral 2 electron donor ligand. When n is 1, E preferably is a -arene ligand such as toluene, benzene, and mesitylene. When n is 2, E is preferably selected from diethylether, tetrahrydrofuran (THF), and dioxane. The ratio of monomer to catalyst in the reaction medium can range from about 2000:1 to about 100:1. The reaction can be run in a hydrocarbon solvent such as cyclohexane, toluene, and the like at a temperature range from about 0xc2x0 C. to about 70xc2x0 C., preferably 10xc2x0 C. to about 50xc2x0 C., and more preferably from about 20xc2x0 C. to about 40xc2x0 C. Preferred catalysts of the above formula are (toluene)bis(perfluorophenyl) nickel, (mesitylene)bis(perfluorophenyl) nickel, (benzene)bis(perfluorophenyl) nickel, bis(tetrahydrofuran)bis(perfluorophenyl) nickel and bis(dioxane)bis(perfluorophenyl) nickel.
The multicomponent catalyst system embodiment of the present invention comprises a Group VIII metal ion source, in combination with one or both of an organometal cocatalyst and a third component. The cocatalyst is selected from organoaluminum compounds, dialkylaluminum hydrides, dialkyl zinc compounds, dialkyl magnesium compounds, and alkyllithium compounds.
The Group VIII metal ion source is preferably selected from a compound containing nickel, palladium, cobalt, iron, and ruthenium with nickel and palladium being most preferred. There are no restrictions on the Group VIII metal compound so long as it provides a source of catalytically active Group VIII metal ions. Preferably, the Group VIII metal compound is soluble or can be made to be soluble in the reaction medium.
The Group VIII metal compound comprises ionic and/or neutral ligand(s) bound to the Group VIII metal. The ionic and neutral ligands can be selected from a variety of monodentate, bidentate, or multidentate moieties and combinations thereof.
Representative of the ionic ligands that can be bonded to the metal to form the Group VIII compound are anionic ligands selected from the halides such as chloride, bromide, iodide or fluoride ions; pseudohalides such as cyanide, cyanate, thiocyanate, hydride; carbanions such as branched and unbranched (C1 to C40) alkylanions, phenyl anions; cyclopentadienylide anions; -allyl groupings; enolates of -dicarbonyl compounds such as acetylacetonate (4-pentanedionate), 2,2,6,6-tetramethyl-3,5-heptanedionate, and halogenated acetylacetonoates such as 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, 1,1,1-trifluoro-2,4,pentanedionate; anions of acidic oxides of carbon such as carboxylates and halogenated carboxylates (e.g., acetates, 2-ethylhexanoate, neodecanoate, trifluoroacetate, etc.) and oxides of nitrogen (e.g., nitrates, nitrites, etc.) of bismuth (e.g., bismuthate, etc.), of aluminum (e.g., aluminates, etc.), of silicon (e.g., silicate, etc.), of phosphorous (e.g., phosphates, phosphites, phosphines, etc.) of sulfur (e.g., sulfates such as triflate, p-toluene sulfonate, sulfites, etc.); ylides; amides; imides; oxides; phosphides; sulfides; (C6 to C24) aryloxides, (C1 to C20) alkoxides, hydroxide, hydroxy (C1 to C20) alkyl; catechols; oxalate; chelating alkoxides and aryloxides. Palladium compounds can also contain complex anions such as PFxe2x88x926, AlF3O3SCFxe2x88x923, SbFxe2x88x926 and compounds represented by the formulae:
Al(Rxe2x80x2xe2x80x3)xe2x88x924, B(X)xe2x88x924
wherein Rxe2x80x2xe2x80x3 and X independently represent a halogen atom selected from Cl, F, I, and Br, or a substituted or unsubstituted hydrocarbyl group. Representative of hydrocarbyl are (C1 to C25) alkyl such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonodecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, and isomeric forms thereof; (C2 to C25) alkenyl such as vinyl, allyl, crotyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, pentacosenyl, and isomeric forms thereof. (C6 to C25) aryl such as phenyl, tolyl, xylyl, naphthyl, and the like; (C7 to C25) aralkyl such as benzyl, phenethyl, phenpropyl, phenbutyl, phenhexyl, napthoctyl, and the like; (C3 to C8) cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, 2-norbornyl, 2-norbornenyl, and the like. In addition to the above definitions X represents the radical: 
The term xe2x80x9csubstituted hydrocarbylxe2x80x9d means the hydrocarbyl group as previously defined wherein one or more hydrogen atoms have been replaced with a halogen atom such as Cl, F, Br, and I (e.g., as in the perfluorophenyl radical); hydroxyl; amino; alkyl; nitro; mercapto, and the like.
The Group VIII metal compounds can also contain cations such as, for example, organoammonium, organoarsonium, organophosphonium, and pyridinium compounds represented by the formulae:
A+(R28)4

wherein A represents nitrogen, arsenic, and phosphorous and the R28 radical can be independently selected from hydrogen, branched or unbranched (C1 to C10) alkyl, branched or unbranched (C2 to C20) alkenyl, and (C5 to C16) cycloalkyl, e.g., cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like. R29 and R30 are independently selected from hydrogen, branched and unbranched (C1 to C50) alkyl, linear and branched (C2 to C50) alkenyl and (C5 to C16) cycloalkyl groups as defined above; and n is 1 to 5, preferably n is 1, 2, or 3, most preferably n is 1. The R30 radicals preferably are attached to positions 3, 4, and 5 on the pyridine ring.
It should be noted that increasing the sum of the carbon atoms contained in the R28 radicals confers better solubility of the transition metal compound in organic media such as organic solvents and polycyclic the monomer. Preferably, the R28 radicals are selected from (C1 to C18) alkyl groups wherein the sum of carbon atoms for all R28 radicals is 15 to 72, preferably 25 to 48, more preferably 21 to 42. The R21 radical is preferably selected from linear and branched (C1 to C50) alkyl, more preferably (C10 to C40) alkyl. R30 is preferably selected from linear and branched (C1 to C40) alkyl, more preferably (C2 to C30) alkyl.
Specific examples of organoanumonium cations include tridodecylammonium, methyltricaprylammonium, tris(tridecyl)ammonium and trioctylammonium. Specific examples of organoarsonium and organophosphonium cations include tridodecylarsonium and phosphonium, methyltricaprylarsonium and phosphonium, tris(tridecyl)arsonium and phosphonium, and trioctylarsonium and phosphonium. Specific pyridinium cations include eicosyl-4-(1-butylpentyl)pyridinium, docosyl-4-(13-pentacosyl)pyridinium, and eicosyl-4-(1-butylpentyl)pyridinium.
Suitable neutral ligands which can be bonded to the palladium transition metal are the olefins; the acetylenes; carbon monoxide; nitric oxide, nitrogen compounds such as ammonia, alkylisocyanide, alkylisocyanate, alkylisothiocyanate; pyridines and pyridine derivatives (e.g., 1,10-phenanthroline, 2,2xe2x80x2-dipyridyl), 1,4-dialkyl-1,3-diazabutadienes, 1,4-diaryl-1,3-diazabutadienes and amines such as represented by the formulae: 
wherein R31 is independently hydrocarbyl or substituted hydrocarbyl as previously defined and n is 2 to 10. Ureas; nitriles such as acetonitrile, benzonitrile and halogenated derivatives thereof; organic ethers such as dimethyl ether of diethylene glycol, dioxane, tetrahrydrofuran, furan diallyl ether, diethyl ether, cyclic ethers such as diethylene glycol cyclic oligomers; organic sulfides such as thioethers (diethyl sulfide); arsines; stibines; phosphines such as triarylphosphines (e.g., triphenylphosphine), trialkylphosphines (e.g., trimethyl, triethyl, tripropyl, tripentacosyl, and halogenated derivatives thereof), bis(diphenylphosphino)ethane, bis(diphenylphosphino)propane, bis(dimethylphosphino)propane, bis(diphenylphosphino)butane, (S)-(xe2x88x92)2,2xe2x80x2-bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl, (R)-(+)-2,2xe2x80x2-bis(diphenylphosphino)-1,1xe2x80x2-binaphthyl, and bis(2-diphenylphosphinoethyl)phenylphosphine; phosphine oxides, phosphorus halides; phosphites represented by the formula:
P(OR31)3
wherein R31 independently represents a hydrocarbyl or substituted hydrocarbyl as previously defined; phosphorus oxyhalides; phosphonates; phosphonites, phosphinites, ketones; sulfoxides such as (C1 to C20) alkylsulfoxides; (C6 to C20) arylsulfoxides, (C7 to C40) alkarylsulfoxides, and the like. It should be recognized that the foregoing neutral ligands can be utilized as optional third components as will be described hereinbelow.
Examples of Group VIII transition metal compounds suitable as the Group VIII metal ion source include: palladium ethylhexanoate, trans-Pd Cl2(PPh3)2, palladium (II) bis(trifluoroacetate), palladium (II) bis(acetylacetonate), palladium (II) 2-ethylhexanoate, Pd(acetate)2(PPh3)2, palladium (II) bromide, palladium (II) chloride, palladium (II) iodide, palladium (II) oxide, monoacetonitriletris(triphenylphosphine) palladium (II) tetrafluoroborate, tetrakis(acetonitrile) palladium (II) tetrafluoroborate, dichlorobis(acetonitrile) palladium (II), dichlorobis(triphenylphosphine) palladium (II), dichlorobis(benzonitrile) palladium (II), palladium acetylacetonate, palladium bis(acetonitrile) dichloride, palladium bis(dimethylsulfoxide) dichloride, nickel acetylacetonates, nickel carboxylates, nickel dimethylglyoxime, nickel ethylhexanoate, NiCl2(PPh3)2, NiCl2(PPh2CH2)2, (P(cyclohexyl)3)H Ni(Ph2P(C6H4)CO2), (PPh3) (C6H5)Ni(Ph2PCHxe2x95x90C(O)Ph), bis(2,2,6,6-tetramethyl-3,5-heptanedionate) nickel (II), nickel (II) hexafluoroacetylacetonate tetrahrydrate, nickel (II) trifluoroacetylacetonate dihydrate, nickel (II) acetylacetonate tetrahrydrate, nickelocene, nickel (II) acetate, nickel bromide, nickel chloride, dichlorohexyl nickel acetate, nickel lactate, nickel oxide, nickel tetrafluoroborate, bis(allyl)nickel, bis(cyclopentadienyl)nickel, cobalt neodecanoate, cobalt (II) acetate, cobalt (II) acetylacetonate, cobalt (III) acetylacetonate, cobalt (II) benzoate, cobalt chloride, cobalt bromide, dichlorohexyl cobalt acetates, cobalt (II) stearate, cobalt (II) tetrafluoroborate, iron napthenate, iron (II) chloride, iron (III) chloride, iron (II) bromide, iron (III) bromide, iron (II) acetate, iron (III) acetylacetonate, ferrocene, ruthenium tris(triphenylphosphine) dichloride, ruthenium tris(triphenylphosphine) hydrido chloride, ruthenium trichloride, ruthenium tetrakis(acetonitrile) dichloride, ruthenium tetrakis(dimethylsulfoxide) dichloride, rhodium chloride, rhodium tris(triphenylphosphine) trichloride.
The organoaluminum component of the multicomponent catalyst system of the present invention is represented by the formula:
xe2x80x83AIR323xe2x88x92xQx
wherein R32 independently represents linear and branched (C1 to C20) alkyl, (C6 to C24) aryl, (C7 to C20) aralkyl, (C3 to C10) cycloalkyl; Q is a halide or pseudohalide selected from chlorine, fluorine, bromine, iodine, linear and branched (C1 to C20) alkoxy, (C6 to C24) aryloxy; and x is 0 to 2.5, preferably 0 to 2.
Representative organoaluminum compounds include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-methylhexylaluminum, trioctylaluminum, tris-2-norbornylaluminum, and the like; dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, and the like; monoalkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum diiodide, propylaluminum dichloride, isopropylaluminum dichloride, butylaluminum dichloride, isobutylaluminum dichloride, and the like; and alkylaluminum sesquihalides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, propylaluminum sesquichloride, isobutylaluminum sesquichloride, and the like.
The dialkylaluminum hydride is selected from linear and branched (C1 to C10) dialkylaluminum hydride, with diisobutylaluminum hydride being a preferred dialkylaluminum hydride compound.
The dialkyl zinc compounds are selected from linear and branched (C1 to C10) dialkyl zinc compounds with diethyl zinc being preferred. The dialkyl magnesium compounds are selected from linear and branched (C1 to C10) dialkyl magnesium with dibutyl magnesium being the most preferred. The alkyl lithiums are selected from linear and branched (C1 to C10) alkyl lithium compounds. Butyllithium is the preferred alkyl lithium.
In the practice of the present invention, the catalytic system obtained from the Group VIII metal ion source is utilized with one or both of a component selected from the group of cocatalyst compounds, and third component compounds.
Examples of third components are Lewis acids such as the BF3.etherate, TiCl4, SbF5, tris(perfluorophenyl)boron, BCl3, B(OCH2CH3)3; strong Brxc3x8nsted acids such as hexafluoroantimonic acid (HSbF6), HPF6 hydrate, trifluoroacetic acid (CF3CO2H), and FSO3H.SbF5, H2C(SO2CF3)2CF3SO3H, and paratoluenesulfonic acid; halogenated compounds such as hexachloroacetone, hexafluoroacetone, 3-butenoic acid-2,2,3,4,4-pentachlorobutylester, hexafluoroglutaric acid, hexafluoroisopropanol, and chloranil, i.e., 
electron donors such as phosphines and phosphites and olefinic electron donors selected from (C4 to C12) aliphatic and (C6 to C12) cycloaliphatic diolefins, such as butadiene, cyclooctadiene, and norbornadiene.
Acidity of strong Brxc3x8nsted acids can be gauged by determining their Hammett acidity function H0. A definition of the Hammett acidity function is found in Advanced Inorganic Chemistry by F. A. Cotton and G. Wilkinson, Wiley-Interscience, 1988, p. 107.
As set forth above the neutral ligands can be employed as optional third components with electron donating properties.
In one embodiment of the invention, the multicomponent catalyst system can be prepared by a process which comprises mixing the catalyst components, i.e., the Group VIII metal compound, the cocatalyst compound, and third component (if employed), together in a hydrocarbon or halohydrocarbon solvent and then mixing the premixed catalyst system in the reaction medium comprising at least one silyl functional polycyclic monomer. Alternatively, (assuming the optional third component is utilized), any two of the catalyst system components can be premixed in a hydrocarbon or halohydrocarbon solvent and then introduced into the reaction medium. The remaining catalyst component can be added to the reaction medium before or after the addition of the premixed components.
In another embodiment, the multicomponent catalyst system can be prepared in situ by mixing together all of the catalyst components in the reaction medium. The order of addition is not important.
In one embodiment of the multicomponent catalyst system of the present invention, a typical catalyst system comprises a Group VIII transition metal salt, e.g., nickel ethylhexanoate, an organoaluminum compound, e.g., triethylaluminum, and a mixture of third components, e.g., BF3.etherate and hexafluoroantimonic acid (HSbF6), in a preferred molar ratio of Al/BF3.etherate/Ni/acid of 10/9/1/0.5-2. The reaction scheme is written as follows:
nickel ethylhexanoate+HSbF6+9BF3.etherate+10 triethylaluminumxe2x86x92Active Catalystxe2x80x83xe2x80x831.
In another embodiment of the multicomponent catalyst system of the invention, the catalyst system comprises a nickel salt, e.g., nickel ethylhexanoate, an organoaluminum compound, e.g., triethylaluminum, and a third component Lewis acid, e.g., tris(perfluorophenyl)boron as shown in the following scheme:
nickel ethylhexanoate+tris(perfluorophenyl)boron+triethylaluminumxe2x86x92Active Catalystxe2x80x83xe2x80x832.
In another embodiment of the multicomponent catalyst system of the invention the third component is a halogenated compound selected from various halogenated activators. A typical catalyst system comprises a Group VIII transition metal salt, an organoaluminum, and a third component halogenated compound as shown below:
nickel ethylhexanoate+triethylaluminum+chloranilxe2x86x92Active Catalystxe2x80x83xe2x80x833.
In still another embodiment of the multicomponent catalyst system of this invention no cocatalyst is present. The catalyst system comprises a Group VIII metal salt (e.g. 3-allylnickelbromide dimer and a Lewis acid (e.g. tris(perfluorophenyl)boron as shown below:
xcex73-allylnickel chloride+tris(perfluorophenyl)boronxe2x86x92Active Catalystxe2x80x83xe2x80x834.
We have found that the choice of Group VIII metal in the metal cation complex of both the single and multicomponent catalyst systems of this invention influences the microstructure and physical properties of the polymers obtained. For example, we have observed that palladium catalysts typically afford norbornene units which are exclusively 2,3 enchained and showing some degree of tacticity. The polymers catalyzed by the type 2 catalyst systems and the single component catalyst systems of the formula EnNi(C6F5)2 described above contain a perfluorophenyl group at least one of the two terminal ends of the polymer chain. In other words, a perfluorophenyl moiety can be located at one or both terminal ends of the polymer. In either case the perfluorophenyl group is covalently bonded to and pendant from a terminal polycyclic repeating unit of the polymer backbone.
Reactions utilizing the single and multicomponent catalysts of the present invention are carried out in an organic solvent which does not adversely interfere with the catalyst system and is a solvent for the monomer. Examples of organic solvents are aliphatic (non-polar) hydrocarbons such as pentane, hexane, heptane, octane and decane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, chlorobenzene, o-dichlorobenzene, toluene, and xylenes; halogenated (polar) hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 2-chloropropane, 1-chlorobutane 2-chlorobutane, 1-chloro-2-methylpropane, and 1-chloropentane.
The choice of reaction solvent is made on the basis of a number of factors including the choice of catalyst and whether it is desired to run the polymerization as a slurry or solution process. For most of the catalysts described in this invention, the preferred solvents are chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane and aromatic hydrocarbons such as chlorobenzene and nitrobenzene, with simple hydrocarbons being less preferred due to the resulting lower conversion of the functional NB-type monomer(s). Surprisingly we have discovered that certain of the catalyst systems, most notably the multicomponent catalysts based on Group VIII metal compounds and alkylaluminum halides, specifically, monoalkylaluminum dihalides, (e.g., ethylaluminum dichloride), and the type 2 catalysts referred to above also give excellent results (and high monomer conversion) when run in simple hydrocarbons such as heptane, cyclohexane, and toluene.
The molar ratio of total monomer to Group VIII metal for the single and multicomponent catalysts can run from 20:1 to 100,000:1, preferably 50:1 to 20,000:1, and most preferably 100:1 to 10,000:1.
In the multicomponent catalyst systems, the cocatalyst metal (e.g., aluminum, zinc, magnesium, and lithium) to Group VIII metal molar ratio ranges from less than or equal to 100:1, preferably less than or equal to 30:1, and most preferably less than or equal to 20:1.
The third component is employed in a molar ratio to Group VIII metal ranging from 0.25:1 to 20:1. When acids are employed as third components, the acid to Group VIII metal range is less than or equal to 4:1, preferably less than or equal to 2:1.
The temperature at which the polymerization reactions of the present invention are carried out typically ranges from xe2x88x92100xc2x0 C. to 120xc2x0 C., preferably xe2x88x9260xc2x0 C. to 90xc2x0 C., and most preferably xe2x88x9210xc2x0 C. to 80xc2x0 C.
The optimum temperature for the present invention is dependent on a number of variables, primarily the choice of catalyst and the choice of reaction diluent. Thus, for any given polymerization the optimum temperature will be experimentally determined taking these variables into account. In the course of developing these catalyst and polymer systems we have observed that the palladium-carbon bond which links the palladium catalysts to the growing polymer chain is particularly stable. This is a major benefit in polymerizing polycyclic monomers bearing acid labile groups, esters and carboxylic acid functionalities since the palladium catalysts are extremely tolerant to such functionalities. However, this stability also makes it very difficult to remove the palladium catalyst residues from the resulting polymer. During the development of these new compositions, we discovered that the palladium-carbon bond can be conveniently cleaved (resulting in precipitation of palladium metal which can be removed by filtration or centrifugation) using carbon monoxide, preferably in the presence of a protic solvent such as an alcohol, moisture, or a carboxylic acid.
The polymers obtained by the process of the present invention are produced in a molecular weight (Mn) range from about 1,000 to about 1,000,000, preferably from about 2,000 to about 700,000, and more preferably from about 5,000 to about 500,000 and most preferably from about 10,000 to about 50,000.
Molecular weight can be controlled by changing the catalyst to monomer ratio, i.e., by changing the initiator to monomer ratio. Lower molecular weight polymers and oligomers may also be formed in the range from about 500 to about 500,000 by carrying out the polymerization in the presence of a chain transfer agent. Macromonomers or oligomers comprising from 4 to 50 repeating units can be prepared in the presence of a CTA (Chain Transfer Agent) selected from a compound having a terminal olefinic double bond between adjacent carbon atoms, wherein at least one of the adjacent carbon atoms has two hydrogen atoms attached thereto. The CTA is exclusive of styrenes (non-styrenes), vinyl ethers (non-vinyl ether) and conjugated dienes. By non-styrenic, non-vinyl ether is meant that compounds having the following structures are excluded from the chain transfer agents of this invention: 
wherein A is an aromatic substituent and R is hydrocarbyl.
The preferred CTA compounds of this invention are represented by the following formula: 
wherein Rxe2x80x2 and Rxe2x80x3 independently represent hydrogen, branched or unbranched (C1 to C40) alkyl, branched or unbranched (C2 to C40) alkenyl, and halogen.
Of the above chain transfer agents the olefins having 2 to 10 carbon atoms are preferred, e.g., ethylene, propylene, 4-methyl-1-pentene, 1-hexene, 1-decene, 1,7-octadiene, and 1,6-octadiene, or isobutylene.
While the optimum conditions for any given result should be experimentally determined by a skilled artisan taking into the account all of the above factors there are a number of general guidelines which can be conveniently utilized where appropriate. We have learned that, in general, -olefins (e.g., ethylene, propylene, 1-hexene, 1-decene, 4-methyl-1-pentene) are the most effective chain transfer agents with 1,1-disubstituted olefins (e.g., isobutylene) being less efficient. In other words, all other things being equal, the concentration of isobutylene required to achieve a given molecular weight will be much higher than if ethylene were chosen. Styrenic olefins, conjugated dienes, and vinyl ethers are not effective as chain transfer agents due to their propensity to polymerize with the catalysts described herein.
The CTA can be employed in an amount ranging from about 0.10 mole % to over 50 mole % relative to the moles of total NB-type monomer. Preferably, the CTA is employed in the range of 0.10 to 10 mole %, and more preferably from 0.1 to 5.0 mole %. As discussed above, depending on catalyst type and sensitivities, CTA efficiencies and desired end group, the concentration of CTA can be in excess of 50 mole % (based on total NB-functional monomer present), e.g., 60 to 80 mole %. Higher concentrations of CTA (e.g., greater than 100 mole %) may be necessary to achieve the low molecular weight embodiments of this invention such as in oligomer and macromonomer applications. It is important and surprising to note that even such high concentrations the CTA""s (with the exception of isobutylene) do not copolymerize into the polymer backbone but rather insert as terminal end-groups on each polymer chain. Besides chain transfer, the process of the present invention affords a way by which a terminal -olefinic end group can be placed at the end of a polymer chain.
Polymers of the present invention that are prepared in the presence of the instant CTA""s have molecular weights (Mn) ranging from about 1,000 to about 500,000, preferably from about 2,000 to about 300,000, and most preferably from about 5,000 to about 200,000.